Amide-modified urethane acrylate radiation curable compounds and coating compositions and methods of making same

ABSTRACT

Radiation curable compounds are disclosed comprising an amide moiety, a urethane moiety and an ethylenically unsaturated functional group, typically an acrylate functional group. The compounds comprise the reaction products of an amide-containing compound having at least one hydroxy functional group, a polyisocyanate and a polyfunctional compound having a hydroxy functional group reactive with an isocyanato group of the polyisocyanate, which polyfunctional compound provides an ethylenic functional group in the reaction product. Coating compositions containing these radiation curable reaction products cure at relatively high rates to form films having high abrasion resistance and improved tensile strength and elongation properties as compared to conventional urethane acrylate coating compositions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Radiation sensitive compounds which polymerize rapidly in the presenceof actinic or ionizing radiation are of interest for use in film-formingcompositions. Of particular interest are fast-curing compounds whichprovide elastomeric and wearlayer films having improved durability andflexibility.

2. Description of the Prior Art

Film-forming compositions containing radiation curable components arewell-known. Films formed from compounds having urethane moieties andacrylate functional groups are recognized to possess good wear andweather resistance properties and also have good flexural strengthproperties. Typical of these urethane-acrylate radiation-curablefilm-forming materials are the compositions disclosed in U.S. Pat. No.3,509,234 to Burlant et al and U.S. Pat. No. 4,038,257 to Suzuki et al.Although these urethane acrylate compositions have gained widespreadacceptance for forming protective and decorative films on a variety ofsubstrates, there is ever increasing demand for compositions which curequickly to form tough, flexible films. The advantages of shorter curingtimes include productivity increases coupled with potential savings inenergy consumption. Moreover, a composition which cures quickly afterapplication to a substrate is likely to form a cured coating of highergloss and smoothness inasmuch as the wet film is exposed for a lesserperiod of time to contamination from dust-laden environments typicallyattending coating operations.

Coating compositions containing very fast curing components have beendevised. For example, U.S. application Ser. No. 821,856, filed Aug. 7,1977, of G. W. Gruber, discloses coating compositions containing amidemoieties and acrylate functional groups that can form very hard films oncoated substrates passing under a curing radiation source at about 350feet per minute. These amide acrylate compounds do not, however, providecured films having particularly good flexural strength properties.

Fast-curing compositions for forming tough, flexible protective ordecorative films would be quite useful for coating floor tile, vinyloverlays used in covering furniture and other articles, and variousother flexible substrates. Baseboard coving, for example, is typicallymade of rubber or flexible plastic materials which require protectivefilms of good flexibility since the coving materials are frequentlyshipped in rolls and are folded or bent during application to a wallbase. Vinyl overlay coverings, often only two to ten thousandths of aninch in thickness, are frequently used to cover furniture and otherarticles having sharp-angled surface configurations. Protective filmsfor these vinyl coverings must have sufficient flexural and tensilestrength properties to withstand folding and creasing without the filmcracking, tearing or lifting from the vinyl substrate.

SUMMARY OF THE INVENTION

It has now been found that relatively fast-curing coating compositionsthat form films of improved flexural or tensile strength may be providedby having present in the compositions at least one additionpolymerizable, radiation curable compound containing at least one amidegroup, at least one urethane group and at least one ethylenicallyunsaturated functional group. Each member of the preferred class ofthese amide urethane acrylate compounds comprises the addition reactionproduct of the components of (a) an amide-containing compound having atleast one hydroxy functional group, (b) a polyisocyanate and (c) apolyfunctional compound containing at least one functional groupreactive with an isocyanato group of the polyisocyanate and whichpolyfunctional compound provides at least one ethylenically unsaturatedfunctional group in the reaction product.

In addition to having improved physical strength properties, filmsformed from compositions having one or more of the described additionpolymerizable compounds generally exhibit good elongation properties.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The addition polymerizable radiation curable compound derived from theaddition reaction of an amide compound containing a hydroxy functionalgroup, a polyisocyanate and the described polyfunctional compound may begenerally characterized as an amide urethane acrylate reaction productin that the product comprises molecules having at least one each of anamide group, a urethane group and an acrylate group. In the presence ofactinic light or ionizing radiation, the acrylate groups of themolecules cross-link to form durable, abrasion-resistant films builtfrom a network of molecular units containing the amide and urethanemoieties. Addition polymerization of the amide urethane acrylatecompounds may also be accomplished by heat or by free radical-generatingperoxide catalysts. It is believed that the improved flexural strengthproperties of films made from compositions containing amide urethaneacrylate compounds is due to the presence in the film network ofurethane groups which provide flexibility. Wear-resistance properties ofthe film are believed attributable to the presence of amide groups.

The term "amide hydroxy compound" as used hereinafter is intended as anabbreviated expression for an amide-containing compound having at leastone hydroxy functional group. Suitable amide hydroxy compounds forpreparing the amide urethane acrylate reaction product may be selectedfrom such general classes of compounds as (a) a reaction product of amonocarboxylic acid and an aminoalcohol, (b) a reaction product of anester of a carboxylic acid and an aminoalcohol, (c) a reaction productof a hydroxy carboxylic acid and a compound containing at least oneprimary or secondary amino nitrogen, (d) a reaction product of an innerester of a hydroxy carboxylic acid, such as lactone, and ammonia or acompound containing at least one primary or secondary amino nitrogen,and (e) a polyamide polyol.

Where the amide hydroxy compound is prepared from the reaction of amonocarboxylic acid and an aminoalcohol, the monocarboxylic acid may beany organic acid having one carboxyl group attached to either analiphatic group or an aryl group; the organic portion of the acid may befully saturated or may contain unsaturated groups. The aliphatic andaryl groups may be substituted or unsubstituted. Typically suitablemonocarboxylic acids include formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid,oleic acid, linoleic acid, linolenic acid, cyclohexane-carboxylic acid,phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluicacid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid,o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, salicylicacid, p-hydroxybenzoic acid, anthranilic acid, o-methoxybenzoic acid,m-methoxybenzoic acid and p-methoxybenzoic acid. Preferredmonocarboxylic acid starting materials are formic acid, acetic acid,propionic acid and benzoic acid.

A second general class of suitable amide hydroxy compounds includes theproducts of the reaction of esters, such as the ester cognates of theaforementioned monocarboxylic acids, with aminoalcohols. Of these estersmethyl formate, ethyl acetate and .[.methyl-2-ethyl.]. .Iadd.methyl2-ethyl-.Iaddend.hexanoate are preferred. Other suitable esters includedicarboxylic acid esters such as dimethyl adipate.

Suitable aminoalcohol compounds for reaction with the aforementionedmonocarboxylic acids, their ester cognates and other esters to formamide hydroxy containing intermediates, include ethanolamine,diethanolamine, N-methylethanolamine, N-ethylethanolamine,N-phenylethanolamine, 2-amino-1-butanol, 4-amino-1-butanol,2-amino-2-ethyl-1,3-propanediol, 6-amino-1-hexanol,2-amino-2(hydroxymethyl)-1,3-propanediol, 2-amino-3-methyl-1-butanol,3-amino-3-methyl-1-butanol, 2-amino-4-methyl-1-pentanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol,5-amino-1-pentanol, 3-amino-1,2-propanediol, 1-amino-2-propanol,3-amino-1-propanol and hydroxyalkyl anilines like p-amino-benzylalcohol. Preferred aminoalcohols are ethanolamine, diethanolamine andN-methylethanolamine.

A third case of amide hydroxy compounds includes the reaction productsof a hydroxy carboxylic acid and a compound containing at least oneprimary or secondary amino nitrogen. Suitable hydroxy acids includeα-hydroxy acids such as hydroxyacetic acid, α-hydroxypropionic acid andα-hydroxyisobutyric acid, β-hydroxy acids such as ethyl β-hydroxybutricacid, γ-hydroxy acids such as γ-hydroxyvaleric acid, and aromatichydroxy acids such as mandelic acid. Also suitable is the hydroxy acidprepared from the reaction of phthalic anhydride and diethylene glycol.Preferred hydroxy acids are hydroxyacetic acid and2,2-bis(hydroxymethyl)propionic acid.

An appropriate class of compounds reactable with the aforementionedhydroxy acids, which compounds contain at least one primary or secondaryamino nitrogen, may be drawn from such groups of compounds asaminoalcohols, aminolactams, aliphatic mono- or polyamines and aromaticmono- or polyamines. Suitable aminoalcohols include those set forthabove for reaction with the aforementioned monocarboxylic acid orcarboxylic acid ester starting materials. Examples of suitablealiphatic, cyclic and aromatic amines having at least one labilehydrogen on the nitrogen atom are methylamine, ethylamine,isopropylamine, n-butylamine, hexylamine, neoheptylamine,2-ethyl-hexylamine, decylamine, aminomethyltrimethoxysilane,aminoethyltriethoxysilane, aminoethyltributoxysilane,aminobutyltriethoxysilane, aminopentyltriethoxysilane, aniline,tolylamine, xylylamine, naphthylamine, benzylamine, phenethylamine,cyclopentylamine, methylcyclopentylamine, cyclohexylamine,dimethylcyclohexylamine, dimethylamine, diethylamine, diisopropylamine,dibutylamine, dioctylamine, morpholine, tetrahydrofurfurylamine,piperazine, 2-methylpiperazine, N-methylpiperazine, N-propylpiperazine,piperidine, 2-ethylpiperdine, .[.4,4'-dipiperidyl-1,3-di(4-piperidyl)propane.]. .Iadd.4,4'-dipiperidyl,1,3-di(4-piperidyl)propane.Iaddend., 1,5-di(4-piperidyl)pentane, and thelike. Polyamines are also useful as starting materials to form the amidehydroxy intermediate provided that the polyamine has at least one labilehydrogen on an amino nitrogen atom. Examples of suitable polyamines are.[.polyoxyalkylamines.]. .Iadd.polyoxyalkyleneamines .Iaddend.sold byJefferson Chemical Co. under the trademark Jeffamine ®.

A fourth general class of suitable amide hydroxy compounds includesreaction products of an inner ester of a hydroxy carboxylic acid andammonia or a compound containing at least one primary or secondary aminonitrogen. Useful inner esters of carboxylic acids are lactones, such asγ-butyrolactone, γ-valerolactone, δ-valerolactone and ε-caprolactone.Examples of suitable compounds having a primary or secondary aminonitrogen may be found among the general classes of mono- and diamines.Suitable monoamines are those amines set forth above for reaction withthe aforementioned carboxylic acids. A particularly preferred member ofthis general class of starting materials is the reaction product ofγ-butyrolactone and ethanolamine. This preferred reaction product may beprepared by mixing together equimolar amounts of γ-butyrolactone andethanolamine and heating the mixture to about 190° C. for 24 to 36hours. The reaction product comprises a hydroxy-substituted lactamidentified as N(2-hydroxyethyl)pyrrolidone. Diamines may also be reactedwith one of the aforementioned lactones to form low molecular weightamide hydroxy compounds. Suitable diamines include 1,4-diaminobutane,1,2-diaminocyclohexane, 1,10-diaminodecane, 1,12-diaminododecane,1,6-diaminohexane, 1,5 -diaminopentane, 1,8-diaminooctane,1,2-diamino-2-methylpropane, 1,2-diaminopropane, 1,3-diaminopropane,1,7-diaminoheptane, piperazine and the like.

A fifth class of suitable amide hydroxy compounds includes the reactionproducts of a lactide and a compound containing at least one aminenitrogen that has one or more active hydrogen atoms. Suitable lactidesinclude dilactones formed from the self-esterification of analpha-hydroxy acid. A typically useful lactide is theself-esterification product formed from two moles of lactic acid. Usefulamino nitrogen-containing reactants include ammonia and those compoundsset forth above for making the fourth class of amide hydroxy compounds.

A sixth class of suitable amide hydroxy compounds is provided bypolyamide polyols. Polymeric amides result from the condensationreaction of diamines with diacids as is conventionally known. Preferredpolyamides are those made from reacting saturated polycarboxylic acidswith diamines. Examples of useful saturated polycarboxylic acids areoxalic acid, malonic acid, succinic acid, methylsuccinic acid,2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinicacid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid,2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid,3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebaccic acid, phthalic acid, isophthalic acid,terephthalic acid, tetrachlorophthalic acid, 1,2-hexahydrophthalic acid,1,3-hexahydrophthalic acid, 1,4-hexahydrophthalic acid,1,1-cyclobutanedicarboxylic acid and trans-1,4-cyclohexanedicarboxylicacid. Suitable diamines include those diamines set forth above forreaction with a lactone in the fourth class of amide hydroxy compounds.

In order to provide the essential hydroxyl functionality in theaforementioned polyamides, it may be necessary to react the polyamideswith either hydroxy-containing acids or hydroxy-containing amines,depending on whether an excess of amine or acid monomer is used inmaking the polyamide. Examples of hydroxy-acids include lactic acid,glycolic acid, hydroxy butyric acid, hydroxy stearic acid, recinoleicand the like. Suitable hydroxy-containing amines are aminoalcohols suchas 2-aminoethanol, 2-amino-1-butanol, 4-amino-1-butanol,2-(2-aminoethylamino)-ethanol, 2-amino-2-ethyl-1,3-propanediol,6-amino-1-hexanol, 2-amino-2-(hydroxymethyl)-1,3-propanediol,2-amino-3-methyl-1-butanol, 3-amino-3-methyl-1-butanol,2-amino-4-methyl-1-pentanol, 2-amino-2-methyl-1,3-propanediol,2-amino-2-methyl-1-propanol, 5-amino-1-pentanol,3-amino-1,2-propanediol, 1-amino-2-propanol, 3-amino-1-propanol,2-(3-aminopropylamino)-ethanol, and the like.

Preferred polyamide polyols include polyester amide prepared fromethylene glycol, ethanolamine and adipic acid, and polyester amideprepared from ethylene glycol, ethanolamine and azelaic acid. Otherpreferred classes of polyamide polyols include polyols derived fromcarboxyl or amine terminated polyamide in which the terminal carboxyl oramine groups are reacted with an alkylene oxide such as ethylene oxideor propylene oxide. Especially preferred of these is poly(hexamethyleneadipamide).

Another preferred class of polyamide polyols may be prepared from thecondensation reaction of a polyamine and a polycaprolactone polyol.Suitable polyamines include the diamines and polyalkylamines set forthas starting materials in the aforementioned classes of amide hydroxycompounds. Suitable polycaprolactone polyols are those sold by UnionCarbide Corp. under the trade designation "PCP 0200".

The polyisocyanate compounds useful for making amide urethane acrylatecompound of the invention include ethylene diisocyanate,1,2-diisocyanatopropane, 1,3-diisocyanatopropane,1,6-diisocyanatohexane, trimethylhexamethylene diisocyanate,1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,1,4-diisocyanatocyclohexane, 1,2-diisocyanatododecane,o-diisocyanatobenzene, m-diisocyanatobenzene, p-diisocyanatobenzene,bis(4-isocyanatocyclohexyl)methane, bis(4-isocyanatophenyl)methane,toluene diisocyanate (which commercially is a mixture comprising about80 percent 2,4-diisocyanatotoluene and about 20 percent2,6-diisocyanatotoluene), 3,3'-dichloro-4,4'-diisocyanatobiphenyl,tris(4-isocyanatophenyl)methane, 1,5-diisocyanatonaphthalene,hydrogenated toluene diisocyanate,1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, and1,3,5-tris(6-isocyanatohexyl)-biuret. Also included are polyisocyanatesin a blocked form such as phenyl-blocked toluene diisocyanate andphenyl-blocked diisocyanatonaphthalene.

The third component for making the reaction product of the invention isa polyfunctional compound having at least one functional group which isreactive with an isocyanato group of the aforementioned polyisocyanatecompound. It is further required that the polyfunctional compoundprovide at least one ethylenic functional group in the reaction product.Usually, the functional group of the polyfunctional compound reactivewith the isocyanato group is a hydroxyl group, while the ethylenic groupis furnished by an acrylate moiety. Representative examples of thesepolyfunctional compounds include hydroxy-containing acrylic monomers,such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropylmethacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,4-hydroxybutyl acrylate; and halogenated hydroxyalkyl acrylates such as3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropylmethacrylate, 3-bromo-2-hydroxypropyl acrylate, 3-bromo-2-hydroxypropylmethacrylate, 2-chloro-1-(hydroxymethyl)ethyl acrylate,2-chloro-1-(hydroxymethyl)ethyl methacrylate,2-bromo-1-(hydroxymethyl)ethyl acrylate and2-bromo-1-(hydroxymethyl)ethyl methacrylate.

Other useful polyfunctional compounds include allylic alcohols as aclass.

The reaction product of the invention may be derived by using only oneof the aforementioned polyfunctional compounds or it may be derived froma mixture of more than one compound. The preferred compounds are thehydroxyalkyl acrylic monomers. Especially preferred are 2-hydroxyethylacrylate and 2-hydroxypropyl acrylate.

In addition to the three major components required for preparing theradiation polymerizable compound of the invention, there may beadditional optional components reactable with the major components toform useful reaction products. A fourth component may be ahydroxyfunctional compound, typically a polyol, of low to high molecularweight. The polyol component is useful for modifying the viscosity ofthe amide urethane acrylate compound by increasing the molecular weightof the reaction product without inhibiting its high cure rate or thephysical strength properties of cured films. The polyol generally has anumber of hydroxy functional groups sufficient to react with only aportion of the reactive isocyanato groups of the polyisocyanate to formurethane groups in the reaction product. Thus, the reaction product maycontain a urethane group attached to the residue of the reaction of anamide hydroxy compound with a polyisocyanate and the residue of thereaction of a polyol with a polyisocyanate.

Suitable classes of molecuar weight building polyols having two or morehydroxy functional groups are polyester polyols, simple alkyl diols andtriols, polyether polyols and polyoxyalkylene polyols.

Examples of polyester polyols are the esterification reaction productsof a saturated or unsaturated polycarboxylic acid and an excess ofpolyhydric alcohol. Suitable saturated polycarboxylic acids are setforth above as starting materials for making polyamide polyols. Theethylenically unsaturated polycarboxylic acids include maleic acid,fumaric acid, aconitic acid, itaconic acid, citraconic acid, mesaconicacid, muconic acid and dihydromuconic acid and halo and alkylderivatives of such acids. Mixtures of ethylenically unsaturatedpolycarboxylic acids may be used or only a single such acid may beemployed. The anhydrides of these acids, where the anhydrides exist,are, of course, embraced by the term "acid", since the polyestersobtained therefrom are essentially the same whether the acid oranhydride is used in the reaction.

One or more saturated polycarboxylic acids may optionally be utilized incombination with the ethylenically unsaturated acid or anhydride in thepreparation of unsaturated polyesters. Such acids, especially thesaturated dicarboxylic acids, increase the length of the polyesterwithout adding additional crosslinking sites, which is a desired featurein some polyesters. Saturated tricarboxylic acids and saturated acids ofhigher carboxylic functionality may be used to provide branching wherethis is desirable.

The polyhydric alcohols useful in preparing ethylenically unsaturatedpolyesters include saturated polyhydric alcohols such as ethyleneglycol, 1,3-propanediol, propylene glycol, 2,3-butanediol,1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,9-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane,2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol,3-methyl-pentane-1,4-diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol,diethylene glycol, triethylene glycol, dipropylene glycol, neopentylglycol, glycerol, pentaerythritol, erythritol, sorbitol, mannitol,1,1,1-trimethylolpropane, trimethylolethane, and2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate.Ethylenically unsaturated polyhydric alcohols such as 2-butene-1,4-diolmay be used alone or in admixture with the saturated polyhydricalcohols. Of course, mixtures of saturated polyhydric alcohols ormixtures of unsaturated polyhydric alcohols may be employed.

In addition to the aforementioned polyhydric alcohols, suitablepolyesters may also be formed from reaction of the mentioneddicarboxylic acids with thioether diols such as thiodiethanol or athioether diol made from reaction of 4,4'-dihydroxydiphenyl sulphidewith propylene oxide.

The polyesters derived from reaction of the aforementionedpolycarboxylic acids and polyhydric alcohols should have reactivehydroxy functionality in sterically unhindered positions on thepolyester backbone. Often, such hydroxy functionality is located interminal positions. This may be achieved by reacting a molar excess ofthe alcohol with a carboxyl-terminated acid; or the hydroxyfunctionality may be introduced by capping the polyester with a di- orhigher polyfunctional alcohol which is usually chosen from theaforementioned group of polyhydric alcohols. Other capping compounds forcarboxyl-terminated polyesters include epoxides, such as ethylene oxideand propylene oxide, epihalohydrins such as epichlorohydrin andepibromohydrin, and the triglycerides of epoxidized fatty oils such asepoxidized linseed oil, safflower oil and soybean oil.

Preferred polyester polyols made from reactants described includepoly(hexamethylene adipate), poly(1,4-butylene adipate), poly(ethylenephthalate) and poly(ethylene maleate). Another class of preferredpolyester polyols includes polycaprolactone polyols made frompolymerization of caprolactone with various diols or higher polyols.Especially preferred are those poly(caprolactone) polyols havingmolecular weights in the range of about 500 to 900 and hydroxy values ofabout 180 to 220.

Examples of useful simple alkyl diols and triols as molecular weightbuilding components are the polyhydric alcohols set forth above forpreparation of the polyester polyols. Useful polyether polyols are thoseprepared from the polymerization of aldehydes, alkylene oxides, orglycols by known methods. For example, formaldehyde, ethylene oxide,propylene oxide, epichlorohydrin and the like may addition polymerize toform polyether diols under appropriate conditions. Preferred polyetherpolyols include the class comprising polyalkyleneoxide polyols.Especially preferred are polypropylene glycol, polyethylene glycol andpolybutylene glycol.

The amide urethane acrylate compound of the invention may be generallyprepared by mixing together one or more of each of the aforementionedhydroxy group containing amide compound, polyisocyanate andpolyfunctional compound and allowing the mixture to react for a periodof time sufficient to form the reaction product. Or, an amide-hydroxycompound and a polyisocyanate may be reacted to form an amide urethaneintermediate having at least one terminal isocyanato group; then theintermediate is reacted with the hydroxy acrylate compound. Or, thepolyisocyanate may be reacted with the polyfunctional compound to form aurethaneacrylate intermediate containing at least one terminalisocyanato group; then the intermediate is reacted with an amide-hydroxycompound to form the reaction product. Preferably, the reaction productis formed by firstly preparing an amide-hydroxy intermediate, thensecondly adding the intermediate gradually to the polyisocyanate to forman NCO-terminated amide urethane, and thirdly adding the polyfunctionalcompound gradually to the amide urethane to form an amide urethaneacrylate.

Whether all the components are mixed together at once or the componentsare added together to form intermediates, the equivalent weight ratiosof amidehydroxy compound to polyisocyanate to polyfunctional compoundare generally in the range of 1:1.25:0.25 to 1:2:1, and more usually therange of equivalent weight ratios is 1:1.5:0.65 to 1:2:1, althoughsignificantly lower amounts of the NCO-containing component may be used.An excess of the polyfunctional component is not at all harmful inasmuchas this component, especially when it is one of the aforementionedhydroxy-acrylate compounds, constitutes a reactive diluent for thereaction product.

Where it is desired that the amide urethane acrylate compound beprepared with a molecular weight building polyol component, the polyolmay be reacted with the polyisocyanate in the reaction vessel containingthe amide hydroxy and polyisocyanate components; or the reactions may becarried out in separate vessels, and then the NCO-terminated amideurethane intermediate and the NCO-terminated polyol-residue urethaneintermediate may be mixed together and further reacted with thepolyfunctional compound. It is preferred that a blend of the amidehydroxy component and the polyol component be added gradually to thepolyisocyanate to form a mixture of amide urethane and polyol-residueurethane intermediates.

It is usually desired that the total hydroxy functional group equivalentweight contributed by the amide hydroxy component and the polyolcomponent be somewhat less than the equivalent weight of reactiveisocyanato groups so as to provide NCO reaction sites for thepolyfunctional compound.

The amide urethane acrylate compound may constitute the only majorcomponent of a coating composition or it may be used as an additive tocoating compositions containing other radiation polymerizablecomponents. Typical of these components are polyester, polyurethane andpolyamide materials having ethylenically unsaturated groups capable ofundergoing addition polymerization in the presence of actinic light ofionizing radiation.

Thus, the amide urethane acrylate may be present in coating compositionsin an amount from about 0.1 percent to about 99 percent by weight of thetotal composition. More often the compound is present in a range ofabout 20 to 80 percent. A coating composition may contain the amideurethane acrylate compound alone in a diluent, although other componentsare usually present. The diluent may be of the volatile, non-reactivetype like toluene, xylene or methylene chloride, but is preferred to beof the substantially non-volatile, reactive type such as the classes ofcompounds of monoacrylate and methacrylate esters, diacrylates,acrylamides and heterocyclic vinyl compounds such as N-vinylpyrrolidone. When the reaction product and a reactive diluent make upthe composition, the diluent is usually present in an amount in therange of about 10 to 60 total weight percent, and preferably in therange of about 10 to 20 weight percent.

Examples of preferred radiation polymerizable components which may serveas coreactive diluents are mono- and polyacrylic functional monomerssuch as methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate,octyl methacrylate, neopentyl glycol diacrylate, ethylene glycoldiacrylate, diethylene glycol diacrylate, triethylene glycol diacrylateand tetraethylene glycol diacrylate.

When the coating composition is to be cured by exposure to ultravioletlight, photoinitiator, photosensitizer or a mixture of photoinitiatorand photosensitizer is usually present.

Photoinitiators are compounds which absorb photons and thereby obtainenergy to form radical pairs, at least one of which is available toinitiate addition polymerization of acrylic or methacrylic groups in thewell-known manner. Photosensitizers are compounds which are goodabsorbers of photons, but which are themselves poor photoinitiators.They absorb photons to produce excited molecules which then interactwith a second compound to produce free radicals suitable for initiationof addition polymerization. The second compound may be a monomer, apolymer or an adder initiator. Examples of photoinitiators are benzoin,methyl benzoin ether, butyl benzoin ether, isobutyl benzoin ether,α,α-diethoxyacetophenone and α-chloroacetophenone. Examples ofphotosensitizers are benzil, 1-naphthaldehyde, anthraquinone,benzophenone, 3-methoxybenzophenone, benzaldehyde, diethoxyacetophenoneand anthrone.

The amount of photoinitiator, photosensitizer or mixture ofphotoinitiator and photosensitizer present in the radiation curablecoating composition can vary widely. When any of these materials arepresent, the amount is usually in the range of from about 0.01 to about10 percent by weight of the radiation curable components of the coatingcomposition. Most often the amount is in the range of from about 0.1 toabout 5 percent by weight. When the coating is to be cured by exposureto ionizing radiation, these materials are usually omitted from thecoating composition, although their presence is permissible.

While the preferred method for effecting addition polymerization of thefilm-forming compounds of the invention is by subjecting the compound toan effective dose of ionizing or actinic radiation, other means andmethods may be employed to obtain the desired crosslinked film. Forexample, addition polymerization may be accomplished by the presence ofthermally-sensitive catalysts or initiators which are capable ofgenerating free radicals that may initiate addition polymerization ofthe amide urethane acrylate compound of the invention. Typicalinitiators include benzoyl peroxide and azo bis(isobutyronitrile).

Extender pigments may be present in the composition, and whenultraviolet light is used to cure the film, it is preferred that theextender pigment be substantially transparent to ultraviolet light.Examples of ultraviolet light transparent extender pigments are silica,calcium carbonate, barium sulfate, talc, aluminum silicates, sodiumaluminum silicates and potassium aluminum silicates.

Hiding and/or coloring pigment may optionally be present. When thepigment is of the ultraviolet light absorbing type and the coatingcomposition is to be cured by exposure to ultraviolet light, the pigmentshould be used in amounts which do not preclude curing of the interiorof the coating. Examples of hiding pigments are titanium dioxide,antimony oxide, zirconium oxide, zinc sulfide and lithopone. Examples ofcoloring pigments are iron oxides, cadmium sulfide, carbon black,phthalocyanine blue, phthalocyanine green, indanthrone blue, ultramarineblue, chromium oxide, burnt umber, benzidine yellow, toluidine red andaluminum powder. Individual pigments or mixtures of hiding and/orcoloring pigments may be used.

Mixtures of extender pigments, hiding pigments and/or coloring pigmentsmay also be employed.

Dyes in their customarily used amounts may be present in the coatingcomposition.

Although not ordinarily desired, minor amounts, usually in the range offrom about 0.1 to about 20 percent by weight of the total weight of thecomposition of volatile reactive solvent and/or inert volatile organicorganic solvent may be present in the radiation curable coatingcomposition.

Various additional materials may be added to adjust the viscosity of thecoating compostion. Examples of such materials are fumed silica, castoroil based compositions (e.g., Thixatrol ST, Baker Castor Oil Company),modified clays, 12-hydroxystearic acid, tetrabutyl orthotitanate andmicro-crystalline cellulose. When used, these materials are usuallypresent in an amount in the range of from about 0.5 percent to about 15percent by weight of the radiation curable components.

The radiation curable coating compositions of the invention are usuallyprepared by simply admixing the solution of the amide urethane acrylatecompound dissolved in reactive solvent with such other ingredients asmay be present. Although mixing is usually accomplished at roomtemperature, elevated temperatures are sometimes used. The maximumtemperature which is usable depends upon the heat stability of theingredients. Temperatures above about 120° C. are only rarely employed.

The radiation curable coating compositions are used to form curedadherent coatings on substrates. The substrate is coated with thecoating composition using substantially any technique known to the art.These include spraying, curtain coating, dipping, direct roll coating,reverse roll coating, painting, brushing, printing, drawing andextrusion. The coated substrate is then exposed to radiation tosufficient intensity for a time sufficient to crosslink the coating. Thetimes of exposure to radiation and the intensity of the radiation towhich the coating composition is exposed may vary greatly. Generally,the exposure to radiation should continue until the C-stage is reachedwhen hard, solvent resistant films result. In certain applications,however, it may be desirable for the curing to continue only until theB-stage, viz., gel stage, has been obtained.

Substrates which may be coated with the compositions of this inventionmay vary widely in their properties. Organic substrates such as wood,fiberboard, particle board, composition board, paper, paper board,cardboard and various polymers such as polyesters, polyamides, curedphenolic resins, cured aminoplasts, acrylics, polyurethanes and rubbermay be used. Inorganic substrates are exemplified by glass, quartz andceramic materials. Many metallic substrates may be coated. Exemplarymetallic substrates are iron, steel, stainless steel, copper, brass,bronze, aluminum, magnesium, titanium, nickel, chromium, zinc andalloys. Especially suitable substrates are vinyl overlay coverings whichare typically bonded to furniture and other articles. The amide urethaneacrylate compositions are particularly useful for coating floorcoverings such as tile, asbestos-tile, or linoleum-like coverings, andsuch flexible substrates as wall-base coving. These substrates are madefrom or comprise vinyl-containing polymerizable compositions such asvinyl chloride, vinyl acetate, vinyl fluoride, vinylidene chloride andcopolymerizable combinations of said vinyl-containing compounds withethylene or propylene.

Cured film coatings of the radiation curable coating compositionsusually have thicknesses in the range of from about 0.001 millimeter toabout 3 millimeters. More often they have thicknesses in the range offrom about 0.002 millimeter to about 0.3 millimeter, and most preferredare coatings ranging from 0.002 millimeter to 0.08 millimeter. When theradiation curable coating composition is a radiation curable printingink, the cured coatings usually have thicknesses in the range of fromabout 0.001 millimeter to about 0.003 millimeter.

The coatings of this invention may be cured by exposure to ionizingradiation, the unit of dose of ionizing radiation being the "rad" whichis equal to 100 ergs of energy absorbed from ionizing radiation per gramof material being irradiated. As used throughout the specification, doseis referenced to the bleaching of calibrated blue cellophane filmirrespective of the identity of the coating composition beingirradiated.

The coatings of this invention may also be cured by exposure to actiniclight. Actinic light, as used herein, is electromagnetic radiationhaving a wavelength of 700 nanometers or less which is capable ofproducing, either directly or indirectly, free radicals capable ofinitiating addition polymerization of the coating copositions of theinvention. Usually photoinitiator, photosensitizer or mixtures ofphotoinitiator and photosensitizer are present to absorb photons andproduce the free radicals, although in some cases, these materials arenot needed. Actinic light possesses insufficient energy to produce ionsin a medium composed of common elements such as air or water and hence,has an energy below about 10 electron volts. The most commonly used formof actinic light is ultraviolet light, viz., electromagnetic radiationhaving a wavelength in the range of from about 180 nanometers to about400 nanometers, although actinic light or greater or shorter wave-lengthmay also be used effectively.

Any suitable source which emits ultraviolet light may be used in thepractice of this invention. Suitable sources are set forth in U.S. Pat.No. 4,017,652 to G. W. Gruber.

The times of exposure to actinic light and the intensity of actiniclight to which the coating composition is exposed may vary greatly. Inkeeping with the general principles heretofore set forth, the exposureto actinic light should usually continue until the C-stage is obtained.However, for certain applications, the exposure may be stopped when theB-stage has been achieved.

The following examples setting forth specific reactant quantities andconditions, specify certain additives, such as catalysts, diluents andsurfactants for preparation of the amide urethane acrylate compounds ofthe present invention. Unless otherwise indicated, all parts andpercentages are by weight, and all viscosity values are frommeasurements from the Gardner-Holt viscosity scale. These embodimentsare not to be construed, however, as limiting the invention since thereare numerous variations and modifications possible.

EXAMPLE I

Into a reaction vessel equipped with an agitator, a heater, coolingmeans, a thermometer and refluxing condenser, there is charged 529 partsN-methylethanolamine. The amine is heated to about 99° C. With thetemperature of the amine maintained at 96°-99° C., 615 partsγ-butyrolactone is added gradually to the reaction vessel, approximately9 parts being added every minute. The temperature of the reactionmixture is maintained at 99°-102° C. for about six hours with periodicviscosity checks being made on 100 percent samples. A final viscosity ofR is obtained after which the amide diol intermediate reaction productis cooled to about 52° C. and then placed in a storage container.

Into a reaction vessel equipped as above, there is charged 809 partsbis(4-isocyanatocyclohexyl)methane ("Hylene W"; DuPont), 618 parts2-ethylhexyl acrylate, 0.48 part dibutyltin dilaurate ("Niax" catalyst;Union Carbide Corp.) and 0.05 part phenothiazine. An air sparge isapplied below the surface of the reaction mixture and a nitrogen blanketis established above the mixture. The reaction mixture is heated from21° C. to about 40° C. in a 55-minute period, after which time thenitrogen blanket and air sparge are removed. Then over a two hour periodthere is added to the reaction vessel a blend of 663 parts of apolycaprolactone polyol having a hydroxyl value of 216 (PCP 0200; UnionCarbide Corporation) and 143 parts of the previously prepared amide diolintermediate. The temperature of the reaction mixture is observed tovary during the two-hour addition period from about 42° C. to about 52°C. The reaction mixture is held at about 52° C. for two hours, afterwhich time a viscosity check is made on a sample of the reaction mixturediluted to 75 percent concentration in toluene and is found to be V⁺.The reaction mixture is then heated to about 63° C. and held at thattemperature for one hour and 45 minutes, after which time a viscosity ofV⁺ is obtained for a sample taken as before. The reaction mixture isheated to about 68° C. during a one hour and 5 minute holding period.Then a blend of 4.5 parts hydroxyethyl acrylate and 2.3 partsdi-t-butyl-p-cresol ("Ionol" inhibiting agent; Shell Oil Company) isadded to the reaction vessel. Over a 30-minute period 254 partshydroxyethyl acrylate is added to the reaction mixture, after which timethe temperature is observed to be 69° C. and a viscosity measurement ofV⁺ is obtained for a sample taken as before. The reaction mixture isthen maintained at 76°-76° C. for two hours and 45 minutes during whichtime viscosity measurements of V⁻ and U⁺ are obtained. Then 24.5 partsglacial acrylic acid is added to the reaction mixture and after 45minutes a viscosity of V⁺ is obtained for a sample diluted to 75 percentconcentration in 2-ethoxyethanol. The amide urethane acrylate reactionproduct is cooled to about 52° C. and filtered through a nylon bag intoa storage container.

To 50.0 parts of the previously prepared amide urethane acrylatereaction product is added 2.5 parts of a 60/40 mixture ofbenzophenone/diethoxyacetophenone photocatalyst system to form a coatingcomposition. Three "Bonderite" 37Q steel test panels are manually coatedwith the composition using a 0.008 wire-bound draw-down bar to achieve acoating thickness of 0.2-0.3 mil. The coated panels pass once under abank of four 200-watt per inch mercury vapor lamps spaced at a distanceof about 31/2 inches from the test panels which are transported underthe lamps at conveyor speeds of 60, 80 and 100 feet per minute. Thepanels are then subjected to a fingernail mar test and to a methylethylketone double-rub test. Test results are reported in Table I.

                  TABLE I                                                         ______________________________________                                        Conveyor Speed            Solvent Resistance                                  (Ft./Min.) Mar-Resistance (No. of Double Rubs)                                ______________________________________                                        100        Fair to good   40                                                  80         Good           65                                                  60         Good to very good                                                                            95                                                  ______________________________________                                    

EXAMPLE II

Into a reaction vessel equipped as in Example I, there is charged 360parts bis(4-isocyanatocyclohexyl)methane, 244 parts 2-ethylhexylacrylate and 0.14 part dibutyltin dilaurate. With the reaction mixtureunder slight agitation, there is added gradually over a two-hour perioda blend of 220 parts polyoxybutylene having an average molecular weightof 630 and 59.5 parts of the amide diol intermediate reaction productprepared in Example I. Approximately 23.2 parts of the blend is addedevery 10 minutes during the addition period, with the temperature of thereaction mixture rising initially from about 17° C. to about 32° C. Thereaction mixture is maintained at 50°-54° C. for two hours, then heatedto about 66° C. and held at 66°-67° C. for two hours, after which time aviscosity measurement of G is obtained for a sample diluted to 75percent concentration in toluene. After another one-hour holding period,the temperature of the reaction mixture of about 71° C. is observed anda viscosity measurement of G is obtained as before. Then a slurryconsisting of 4.54 parts hydroxyethyl acrylate and 1.7 partsdi-t-butyl-p-cresol is added quickly to the reaction mixture. Over a30-minute period and with the temperature of the reaction mixturemaintained at about 71° C., 168 parts hydroxyethyl acrylate is graduallyadded to the reaction vessel, approximately 28 parts of the acrylatebeing added every five minutes. After one hour with the temperature ofthe reaction mixture at about 76° C., a viscosity value of J is obtainedas measured before. The temperature of the reaction mixture is then heldfor three more hours at 75°-79° C. with a final viscosity measurement ofM being obtained on a sample diluted to 75 percent concentration in2-ethoxyethanol. The amide urethane acrylate reaction product is cooledto about 40° C. and filtered through a nylon bag into a storagecontainer.

To 50.0 parts of an amide urethane acrylate reaction product prepared asgenerally set forth above, there is added 0.75 part diethoxyacetophenoneto form a rapidly curing coating composition. Commercially available,industrial grade vinyl asbestos tiles are manually coated with thecomposition using a 0.042 wire-wound draw-down bar to achieve a coatingthickness of 2 to 2.5 mil. The coated test tiles are given a threesecond exposure to a "Chromalox" infrared heating element (rated 3200watts/ft.²) at a distance of about two inches from the tiles to promoteflow of the coating composition over the test tiles. Then the tiles areexposed in a nitrogen atmosphere to a bank of two 200-watt per inchmercury vapor lamps spaced at a distance of about 31/2 inches from thetiles which are transported under the lamps at 30 feet per minute.Uniformly glossy and surface-hard film coatings are obtained on each ofthe test tiles.

EXAMPLE III

Into a raction vessel equipped as in Example I, there is charged 150parts N-methylethanolamine. Over a period of about one hour, 172 partsγ-butyrolactone is added dropwise to the reaction vessel with thetemperature of the reaction mixture being maintained at about 100°-103°C. The reaction mixture is then maintained at about 100° C. for onehour, after which time an infrared analysis of the reaction productshows substantially no unreacted γ-butyrolactone in the amide diolintermediate reaction product.

Into another reaction vessel equipped as above, there are charged 532parts bis(4-isocyanatocyclohexyl)methane, 284 parts methylethylketoneand 0.5 part dibutyltin dilaurate. The mixture is heated to about 70° C.with agitation. Over a period of two hours and 10 minutes, a blend of264.5 parts of a polycaprolactone polyol having a hydroxyl value ofabout 212 (PCP 0200; Union Carbide Corp.) and 168 parts of thepreviously prepared amide diol intermediate is added dropwise to thereaction mixture. At the end of the addition period, the temperature ofthe reaction mixture is observed to be about 80° C. Over a 30 minuteperiod, a blend of 174 parts hydroxyethyl acrylate and 2 partsdi-t-butyl-p-cresol is added dropwise to the reaction mixture which ismaintained at a temperature of about 77° C. The reaction mixture is thenheld at about 77° C. for about one hour after which time a viscositymeasurement of X^(+1/2) is obtained on a sample diluted to 75 percentconcentration in 2-ethoxyethanol. An infrared analysis shows very littleunreacted isocyanato group in the amide urethane acrylate reactionproduct.

A sample of the previously prepared amide urethane acrylate reactionproduct is diluted with ethyl acetate to give a coating compositioncomprising about 41 percent solvent. To 50 parts of the coatingcomposition is added 0.5 part diethoxyacetophenone and 5 partsmethylethylketone. Several electrolytic tin plate panels, previouslywiped with acetone, are manually coated with the composition to anapplication thickness sufficient to achieve a cured-film thickness ofabout 2 mils. Then the coated panels are heated at about 52° C. forabout 11/2 hours to remove volatile solvent. The coated panels are thenexposed to curing radiation in a nitrogen atmosphere by passing thepanels twice under a bank of four 200 watt per inch mercury vapor lampspositioned about 31/2 inches above a conveyor transporting the coatedpanels at 70 feet per minute. Hard, glossy, strippable film coatings areformed having tensile and elongation properties as reported in Table II.

EXAMPLE IV

Into a reaction vessel equipped as in Example I, there is charged 230parts of a polyoxyethyleneamine (Jeffamine® D-230; Jefferson ChemicalCo., Inc.). The amine is heated to about 80° C. and over a one-hourperiod 189.2 parts γ-butyrolactone is added dropwise to the reactionvessel. The reaction mixture is heated to about 100° C. and maintainedat that temperature for about one hour and 40 minutes. Since infraredanalysis of the reaction mixture shows carbonyl functional groupindicating the presence of unreacted γ-butyrolactone in the mixture, 15parts more of the polyoxyethyleneamine is added to the reaction vessel.The reaction vessel is allowed to stand overnight, then heated from 28°C. to about 60° C. in 30 minutes, and thereafter held at 55°-60° C. forabout one hour. The reaction mixture is allowed to cool to 45° C. in 30minutes after which time an infrared analysis shows unreactedγ-butyrolactone in the mixture. The reaction mixture is allowed to standfor three days and is then heated and held at about 100° C. for threehours, after which time 15 parts more of the polyoxyethyleneamine isadded. The reaction mixture is heated two more hours at about 100° C.,after which time a satisfactory infrared analysis is obtained showingsubstantially no unreacted γ-butyrolactone in the amide diolintermediate reaction product.

Into another reaction vessel, equipped as before, there are charged 532parts bis(4-isocyanatocyclohexyl)methane, 368 parts methyl isobutylketone and 0.5 part dibutyltin dilaurate. The mixture is heated to about40° C. Over a two-hour period, a blend of 529 parts of apolycaprolactone polyol (PCP 0200, Union Carbide Corp.) and 238 parts ofthe previously prepared amide diol intermediate reaction product isadded dropwise to the reaction mixture. Then 210 parts methyl ethylketone is added to the reaction mixture. The reaction mixture is heatedto about 60° C. in 25 minutes at which time 33 partsbis(4-isocyanatocyclohexyl)methane is added, with the temperaturemaintained thereafter at 60°-70° C. for one hour and 35 minutes. Then ablend of 174 parts hydroxyethyl acrylate and 2 parts di-t-butyl-p-cresolis added to the reaction mixture. After about two hours at 70°-75° C.the reaction mixture is cooled. A viscosity measurement of V⁺ isobtained for a sample of the amide urethane acrylate reaction productdiluted to 75 percent concentration in 2-ethoxyethanol.

A sample of the previously prepared amide urethane acrylate reactionproduct is diluted with ethyl acetate to give a coating compositioncomprising about 41 percent solvent. To a 100 parts of the compositionis added 0.5 part diethoxyacetophenone. Several electrolytic tin platepanels, previously wiped with acetone, are manually coated with thecomposition using three mil bird applicator bar to an applicationthickness sufficient to achieve a cured-film thickness of about 2 mils.Then the panels are heated at about 52° C. for about 11/2 hours toremove volatile solvent. The coated panels are then exposed to curingradiation in a nitrogen atmosphere by passing the panels twice under abank of four 200 watt per inch mercury vapor lamps spaced at a distanceof about 31/2 inches above a conveyor transporting the coated panels at70 feet per minute. Strippable hard, glossy films are formed havingtensile and elongation properties as reported in Table II.

EXAMPLE V

Into a reaction vessel equipped as in Example I there is charged 269parts bis(4-isocyanatocyclohexyl)methane, 192 parts methyl ethyl ketoneand 0.2 part dibutyltin dilaurate. A blend of 119 parts of the amidediol intermediate prepared in Example IV and 107 parts polypropyleneglycol having an average molecular weight of about 440 is added dropwiseto the reaction mixture over a period of two hours, with the temperatureof the reaction mixture being maintained at about 36° C. The reactionmixture is heated to about 80° C. in 15 minutes, then maintained at thattemperature for about 25 minutes, and thereafter allowed to cool andstand overnight. The reaction mixture is then heated and maintained at78°-80° C. for about 21/2 hours. To the reaction mixture is added 1 partdi-t-butyl-p-cresol followed by the dropwise addition of 81.2 partshydroxyethyl acrylate. The reaction mixture is then maintained at75°-77° C. for about 43/4 hours. A sample of the amide urethane acrylatereaction product diluted to 75 percent concentration in 2-ethoxyethanolis observed to have a viscosity of N⁻.

Coating compositions are prepared by the addition of 0.5 partdiethoxyacetophenone to 50 parts of the amide urethane acrylate reactionproduct. Tin-free steel test panels are coated with the composition toan application thickness sufficient to give a cured film thickness ofabout 5 mil. The coated panels are exposed to curing radiation bypassing the panels twice under a bank of four mercury vapor lampspositioned at about 31/2 inches from a conveyor transporting the panelsat 70 feet per minute. After exposure to curing radiation and for thepurpose of driving off residual solvent, the coated panels are baked atabout 71° C. for three hours and then baked at about 49° C. for 18hours. Strippable hard, glossy films are formed having tensileelongation properties as reported in Table II.

EXAMPLE IV

Into a reaction vessel equipped as in Example I, there is charged 75parts N-methylethanolamine. Over a period of about one hour, 86 partsγ-butyrolactone is added dropwise to the reaction vessel with thetemperature of the reaction mixture being maintained at about 100° C.The reaction mixture is then maintained at 100°-105° C. for about fourhours, after which time the reaction mixture is allowed to standovernight. Then after adding about 75 parts N-methylethanolamine to thereaction vessel, the reaction mixture is heated for three more hours atabout 100° C. Infrared analysis indicates presence of unreactedγ-butyrolactone in the amide diol intermediate reaction product.

Into another reaction vessel equipped as before; there are charged 415parts bis(4-isocyanatocyclohexyl)methane, 420 parts methylethylketoneand 0.2 part dibutyltin dilaurate. The mixture is heated to about 40° C.with agitation. Over a two-hour period, a blend of 397 parts of apolycaprolactone polyol (PCP 0200; Union Carbide Corp.) and 92 parts ofthe previously prepared reaction product is added dropwise to thereaction mixture. The temperature of the reaction mixture is thenmaintained at about 80° C. for about 20 minutes, after which time thereaction is allowed to cool and stand for about 41 hours. The reactionmixture is heated to about 80° C. in 50 minutes, and then over a 30minute period, a blend of 85 parts hydroxyethyl acrylate and 2 partsdi-t-butyl-p-cresol is added dropwise to the reaction mixture. Thereaction mixture is then held at about 80° C. for one hour and 40minutes after which time an infrared analysis of the reaction productshows very little unreacted isocyanato group in the amide urethaneacrylate product. A viscosity measurement of Y⁻ is obtained on a sampleof the reation product diluted to 75 percent concentration in2-ethoxyethanol.

A urethane acrylate resin devoid of amide groups is prepared forcomparative testing purposes. Into another reaction vessel equipped asbefore, there are charged 332.5 partsbis(4-isocyanatocyclohexyl)methane, 243 parts methylethylketone and 0.1part dibutyltin dilaurate. The mixture is heated to about 50° C. andover a period of about three hours, 529 parts of a polycaprolactonepolyol having a hydroxyl value of about 212 (PCP0200; Union CarbideCorp.) is added dropwise to the reaction mixture. The reaction mixtureis heated about 65° C. and maintained at that temperature for about 11/2hours. Then over a period of about 40 minutes, a blend of 116 partshydroxyethyl acrylate and 1 part di-t-butyl-p-cresol is added dropwiseto the reaction mixture, after which the temperature of the reactionmixture is observed to be about 68° C. The reaction mixture is allowedto cool and stand overnight. Then the mixture is heated to 67°-68° C.and held at that temperature for about 40 minutes. A viscositymeasurement of Zl⁺ is obtained for a sample of the urethane acrylatereaction product diluted to 75 percent concentration with2-ethoxyethanol.

Coating compositions are prepared by the addition of 0.5 partdiethoxy-acetophenone to 50 parts of each of the amide urethane acrylateand urethane acrylate reaction products. Samples of each coatingcomposition are applied to tin-free steel test panels to an applicationthickness sufficient to provide a cured film thickness of 2 to 4 mil.Some of the test panels coated with amide urethane acrylate compositionand all of the urethane acrylate coated panels are subjected to aninfrared pretreatment to promote levelling of the uncured film coatingon the test panels by baking the coated panels for 11/2 hours at about49° C. Amide urethane acrylate and urethane acrylate coated panelssubjected to the aforementioned pre-treatment are designated as cured byMethod "B", while the other amide urethane acrylate coated panels notsubjected to pre-treatment are designated as cured by Method "A". All ofthe coated test panels are then exposed to curing radiation by passingthe panels twice under a bank of four mercury vapor lamps positioned31/2 inches from a conveyor transporting the panels at 70 feet perminute. After exposure to curing radiation, the amide urethane acrylatecoated panels of Method "A" (but not the amide urethane acrylate coatedpanels of Method "B", nor the urethane acrylate coated panels), arebaked at about 71° C. for three hours and then at about 49° C. for 18hours to drive off residual volatile solvent. Data as to comparativephysical properties of film coatings made from the urethane acrylate andamide urethane acrylate reaction products are set forth in Table II.

                                      TABLE II                                    __________________________________________________________________________                   Average Cured                                                       Resin Reaction                                                                          Film Thickness                                                                        Average Tensile                                                                        Average  Number of                            Example                                                                            Product   (mil)   Strength (p.s.i.)*                                                                     Elongation (%)*                                                                        Replicates                           __________________________________________________________________________    III  Amide Urethane                                                                          2.15    4678     78       2                                         Acrylate                                                                 IV   Amide Urethane                                                                          3.5     3263     201      4                                         Acrylate                                                                 V    Amide Urethane                                                                          5.0     3616     55       3                                         Acrylate                                                                 VI   Urethane Acrylate                                                                       2.78    2133     327      2                                    Meth. A                                                                            Amide Urethane                                                                          3.6     4177     353      5                                         Acrylate                                                                 Meth. B                                                                            Amide Urethane                                                                          2.0     4369     285      4                                         Acrylate                                                                 __________________________________________________________________________     *Tested according to ASTM Method D 68372.                                

Although specific examples of the instant invention have been set forthhereinabove, it is not intended that the invention be limited solelythereto, but is to include all the variations and modifications fallingwithin the scope of the appended claims.

What is claimed:
 1. Addition polymerizable compound having .[.atleast.]. one .Iadd.or two .Iaddend.amide .[.group.]..Iadd.groups.Iaddend., at least .[.one.]. .Iadd.three .Iaddend.urethane.[.group.]. .Iadd.groups .Iaddend.and at least one .[.ethylenicallyunsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.groupcomprising the reaction product of .[.the.]. components .[.of.]..Iadd.comprising: .Iaddend.(a) an amide-containing compound .[.having.]..Iadd.which contains one or two amide groups and .Iaddend.at least oneNCO-reactive hydroxy functional group; (b) a polyisocyanate .Iadd.whichis a diisocyanate or a triisocyanate.Iaddend.; .[.and.]. (c) apolyfunctional compound .[.containing at least one functional groupreactive with an isocyanato group of said polyisocyanate and.]. which.[.polyfunctional compound.]. provides at least one .[.ethylenicallyunsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.groupin said reaction product.Iadd., said polyfunctional compound being ahydroxy-containing ester of acrylic acid or a hydroxy-containing esterof methacrylic acid; and .Iaddend. .Iadd.(d) polyol selected from thegroup consisting of polyester polyol and polyether polyol.Iaddend.. 2.The addition polymerizable compound of claim 1, wherein saidamide-containing compound .[.having at least one hydroxy functionalgroup.]. is selected from the group consisting of(a) a reaction productof a monocarboxylic acid and an aminoalcohol; (b) a reaction product ofan ester of a carboxylic acid and an aminoalcohol; (c) a reactionproduct of a hydroxy carboxylic acid and a compound containing .[.atleast.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]..Iadd.nitrogens.Iaddend.; (d) a reaction product of a lactone andammonia or a compound containing .[.at least.]. one .Iadd.or two.Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.; and (e) areaction product of a lactide and ammonia or a compound containing .[.atleast.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]..Iadd.nitrogens.Iaddend.. .[.
 3. The addition polymerizable compound ofclaim 1, wherein said amide-containing compound having at least onehydroxy functional group is a polyamide polyol..].
 4. The additionpolymerizable compound of claim .[.2.]. .Iadd.1.Iaddend., wherein said.Iadd.amide-containing compound is a reaction product of (a) a.Iaddend.monocarboxylic acid .[.is.]. selected from the group consistingof formic acid, acetic acid, propionic acid and benzoic acid .Iadd.and(b) an aminoalcohol. .Iaddend.
 5. The addition polymerizable compound ofclaim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containingcompound is a reaction product of (a) an .Iaddend.ester of a carboxylicacid .[.is.]. selected from the group consisting of methyl formate,ethyl acetate, dimethyl adipate and .[.methyl-2-ethyl hexanoate.]..Iadd.methyl 2-ethylhexanoate and (b) an aminoalcohol. .Iaddend.
 6. Theaddition polymerizable compound of claim .[.2.]. .Iadd.1.Iaddend.,wherein said .Iadd.amide-containing compound is a reaction product of(a) a .Iaddend.hydroxy carboxylic acid .[.is.]. .Iadd.selected from thegroup consisting of .Iaddend.hydroxyacetic acid,2,2-bis(hydroxymethyl)propionic acid .[.or.]. .Iadd.and .Iaddend.anaromatic hydroxy acid prepared from the reaction of phthalic anhydrideand diethylene glycol .Iadd.and (b) a compound containing one or twoamino nitrogens. .Iaddend.
 7. The addition polymerizable compound ofclaim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containingcompound is a reaction product of (a) a .Iaddend.lactone .[.is.].selected from the group consisting of γ-butyrolactone, γ-valerolactone,δ-valerolactone and ε-caprolactone .Iadd.and (b) a compound containingone or two amino nitrogens. .Iaddend.
 8. The addition polymerizablecompound of claim .[.2.]. .Iadd.6 or 7.Iaddend., wherein said compoundcontaining .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]..Iadd.nitrogens .Iaddend.is selected from the group consisting ofaminoalcohol, aliphatic mono- or .[.polyamine.]. .Iadd.diamine.Iaddend.,aromatic mono- or .[.polyamine.]. .Iadd.diamine .Iaddend.and cyclicmono- or .[.polyamine.]. .Iadd.diamine. .Iaddend.
 9. The additionpolymerizable compound of claim .[.8.]. .Iadd.4 or 5.Iaddend., whereinsaid aminoalcohol .[.that is reactable with one of said carboxylic acid,carboxylic acid ester, hydroxy carboxylic acid, lactone and lactide.].is selected from the group consisting of ethanolamine, diethanolamine,N-methylethanolamine and aminobenzyl alcohol.
 10. The additionpolymerizable compound of claim .[.8.]. .Iadd.6 or 7.Iaddend., whereinsaid .Iadd.compound containing one or two amino nitrogens is an.Iaddend.aliphatic .[.mono- or polyamine is.]. .Iadd.diamine.Iaddend.selected from the group consisting of ethylenediamine,1,2-propylenediamine, 1,3-propylenediamine,N,N-dimethylpropylenediamine, hexamethylenediamine and.[.poly(alkyleneoxide diamines).]. .Iadd.poly(alkyleneoxide) diamine..Iaddend.
 11. The addition polymerizable compound of claim .[.8.]..Iadd.6 or 7.Iaddend., wherein said .[.aromatic mono- or polyamine.]..Iadd.compound containing one or two amino nitrogens .Iaddend.isbenzylamine.
 12. The addition polymerizable compound of claim .[.8.]..Iadd.6 or 7.Iaddend., wherein said .Iadd.compound containing one or twoamino nitrogens is a .Iaddend.cyclic mono- or .[.polyamine is.]..Iadd.diamine .Iaddend.selected from the group consisting of piperazine,piperidine and morpholine. .[.13. The addition polymerizable compound ofclaim 1, wherein said reaction product further comprises a moietyderived from the reaction of said polyisocyanate and a polyol..]. 14.The addition polymerizable compound of claim .[.13,.]. .Iadd.1.Iaddend.wherein said polyol is .[.selected from the group consisting ofa polyester polyol, alkyl diol, alkyl triol and.]. polyoxyalkylenepolyol.
 15. The addition polymerizable compound of claim .[.13,.]..Iadd.1 .Iaddend.wherein said polyol is a poly(caprolactone) polyol. 16.The addition polymerizable compound of claim .[.13 or.]. 1 wherein saidpolyisocyanate is selected from the group consisting of1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, toluenediisocyanate and bis(4-isocyanatocyclohexyl)methane. .[.17. The additionpolymerizable compound of claim 1, wherein said polyfunctional compoundis selected from the group consisting of acrylic acid andhydroxy-containing acrylic ester..].
 18. The addition polymerizablecompound of claim .[.17.]. .Iadd.1.Iaddend., wherein said.[.hydroxy-containing acrylic ester.]. .Iadd.polyfunctional compound.Iaddend.is selected from the group consisting of 2-hydroxyethylacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and2-hydroxypropyl methacrylate.
 19. A coating composition containingaddition polymerizable compound as defined in claim
 1. 20. An article ofmanufacture having a cured film thereon made from the coatingcomposition of claim
 19. 21. The addition polymerizable compound ofclaim .[.2.]. .Iadd.1 .Iaddend.wherein said amide-containing compound.[.having at least one hydroxy functional group.]. is a reaction productof γ-butyrolactone and ethanolamine, and wherein said reaction productof said γ-butyrolactone and ethanolamine comprisesN-(2-hydroxyethyl)pyrrolidone.
 22. A blend of the reaction product ofclaim 1 and the additional reaction product of(a) a polyol; (b) apolyisocyanate; and (c) a polyfunctional compound containing at leastone functional group reactive with an isocyanato group of saidpolyisocyanate and which polyfunctional compound provides at least oneethylenically unsaturated functional group in said additional reactionproduct.
 23. A method for preparing .Iadd.a reaction product comprising.Iaddend.an addition polymerizable compound .[.comprising a reactionproduct.]. .Iadd.having one or two amide groups, at least three urethanegroups and at least one acrylate or methacrylate group.Iaddend., saidmethod comprising reacting together .[.the.]. components .[.of.]..Iadd.comprising: .Iaddend.(a) an amide-containing compound .[.having.]..Iadd.which contains one or two amide groups and .Iaddend.at least oneNCO-reactive hydroxy functional group; (b) a polyisocyanate .Iadd.whichis a diisocyanate or a triisocyanate.Iaddend.; .[.and.]. (c) apolyfunctional compound .[.containing at least one functional groupreactive with an isocyanato group of said polyisocyanate and.]. which.[.polyfunctional compound.]. provides at least one .[.ethylenicallyunsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.groupin said reaction product.[...]..Iadd., said polyfunctional compoundbeing a hydroxy-containing ester of acrylic acid or a hydroxy-containingester of methacrylic acid; and .Iaddend. (d) polyol selected from thegroup consisting of polyester polyol and polyether polyol. .[.24. Themethod of claim 23, wherein said components and a polyol are reacted toprovide in said reaction product a urethane moiety derived from thereaction of said polyisocyanate with said polyol..].
 25. The method ofclaim 23, wherein said reaction product is made by(a) forming a blendcomprising(1) an NCO-terminated intermediate having at least oneurethane group prepared from the reaction of said polyisocyanate andsaid amide-containing compound .[.having at least one NCO-reactivehydroxy functional group.].; and (2) an NCO-terminated intermediatehaving at least one urethane group prepared from the reaction of .[.a.]..Iadd.said .Iaddend.polyol and said polyisocyanate; (b) reacting saidblend of NCO-terminated intermediates with said polyfunctionalcompound,to provide .[.in.]. said reaction product .[.at least one amidegroup, at least one urethane group and at least one ethylenicallyunsaturated functional group.]..
 26. The method of claim 25, whereinsaid reaction product is made by the steps of(a) adding a mixture ofsaid amide-containing compound and said polyol to said polyisocyanate toform said blend comprising NCO-terminated intermediates; and (b) addingsaid polyfunctional compound to said blend of NCO-terminatedintermediates.
 27. The method of claim 26, wherein(a) said mixture isadded gradually to said polyisocyanate; and (b) said polyfunctionalcompound is added gradually to said blend.
 28. The method of claim.[.24.]. .Iadd.23 .Iaddend.or 25, wherein said polyol is .[.selectedfrom the group consisting of polyester polyol, alkyl diol, alkyl trioland.]. polyoxyalkylene polyol.
 29. The method of claim .[.28.]. .Iadd.23or 25.Iaddend., wherein said .[.polyester.]. polyol is apoly(caprolactone) polyol.
 30. The method of claim 23, wherein saidamide-containing compound .[.having at least one hydroxy functionalgroup.]. is selected from the group consisting of(a) a reaction productof a monocarboxylic acid and an aminoalcohol; (b) a reaction product ofan ester of a carboxylic acid and an aminoalcohol; (c) a reactionproduct of a hydroxy carboxylic acid and a compound containing .[.atleast.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]..Iadd.nitrogens.Iaddend.; (d) a reaction product of a lactone andammonia or a compound containing .[.at least.]. one .Iadd.or two.Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.; and (e) areaction product of a lactide and ammonia or a compound containing .[.atleast.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens..Iaddend. .[.31. The method of claim 23, wherein said amide-containingcompound having at least one hydroxy functional group is a polyamidepolyol..].
 32. The method of claim .[.30.]. .Iadd.23.Iaddend., whereinsaid .[.carboxylic.]. .Iadd.amide-containing compound is a reactionproduct of (a) a monocarboxylic .Iaddend.acid .[.is.]. selected from thegroup consisting of formic acid, acetic acid, propionic acid and benzoicacid .Iadd.and (b) an aminoalcohol.Iaddend..
 33. The method of claim.[.30.]. .Iadd.23.Iaddend., wherein said .Iadd.amide-containing compoundis a reaction product of (a) an .Iaddend.ester of a carboxylic acid.[.is.]. selected from the group consisting of methyl formate, ethylacetate, .[.methyl-2-ethyl hexanoate.]. .Iadd.methyl 2-ethylhexanoate.Iaddend.and dimethyl adipate .Iadd.and (b) an aminoalcohol. .Iaddend.The method of claim .[.30.]. .Iadd.23.Iaddend., wherein said.Iadd.amide-containing compound is a reaction product of (a) a.Iaddend.hydroxy carboxylic acid .[.is.]. .Iadd.selected from the groupconsisting of .Iaddend.hydroxyacetic acid,2,2-bis(hydroxymethyl)propionic acid .[.or.]. .Iadd.and .Iaddend.anaromatic hydroxy acid prepared from the reaction of phthalic anhydrideand diethylene glycol .Iadd.and (b) a compound containing one or twoamino nitrogens. .Iaddend.
 35. The method of claim .[.30.]..Iadd.23.Iaddend., wherein said .Iadd.amide-containing compound is areaction product of (a) a .Iaddend.lactone .[.is.]. selected from thegroup consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactoneand ε-caprolactone .Iadd.and (b) a compound containing one or two aminonitrogens. .Iaddend.
 36. The method of claim .[.30.]. .Iadd.34 or35.Iaddend., wherein said compound containing .[.at least.]. one.Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens .Iaddend.isselected from the group consisting of aminoalcohol, aliphatic mono- or.[.polyamine.]. .Iadd.diamine.Iaddend., aromatic mono- or.[.polyamine.]. .Iadd.diamine .Iaddend.and cyclic mono- or.[.polyamine.]. .Iadd.diamine. .Iaddend.
 37. The method of claim.[.36.]. .Iadd.32 or 33.Iaddend., wherein said aminoalcohol .[.that isreactable with one of said carboxylic acid, carboxylic acid ester,hydroxy carboxylic acid, lactone and lactide,.]. is selected from thegroup consisting of ethanolamine, diethanolamine, N-methylethanolamineand aminobenzyl alcohol.
 38. The method of claim .[.36.]. .Iadd.34 or35.Iaddend., wherein said .Iadd.compound containing one or two aminonitrogens is an .Iaddend.aliphatic .[.mono- or polyamine is.]..Iadd.diamine .Iaddend.selected from the group consisting ofethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,N,N-dimethylpropylenediamine, hexamethylenediamine and.[.poly(alkyleneoxide diamines).]. .Iadd.poly(alkyleneoxide) diamine..Iaddend.
 39. The method of claim .[.36.]. .Iadd.34 or 35.Iaddend.,wherein said .[.aromatic mono- or polyamine.]. .Iadd.compound containingone or two amino nitrogens .Iaddend.is benzylamine.
 40. The method ofclaim .[.36.]. .Iadd.34 or 35.Iaddend., wherein said .Iadd.compoundcontaining one or two amino nitrogens is a .Iaddend.cyclic mono- or.[.polyamine is.]. .Iadd.diamine .Iaddend.selected from the groupconsisting of piperazine, piperidine and morpholine.
 41. The method ofclaim 23.[., 24.]. or 25, wherein said polyisocyanate is selected fromthe group consisting of1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, toluenediisocyanate and bis(4-isocyanatocyclohexyl)methane. .[.42. The methodof claim 23 or 25, wherein said polyfunctional compound is selected fromthe group consisting of acrylic acid and hydroxy-containing acrylicester..].
 3. The method of claim .[.42.]. .Iadd.23.Iaddend., whereinsaid .[.hydroxy-containing acrylic ester.]. .Iadd.polyfunctionalcompound .Iaddend.is selected from the group consisting of2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate.
 44. The method of claim.[.30.]. .Iadd.23 .Iaddend.wherein said amide-containing compound.[.having at least one hydroxy functional group.]. is a reaction productof γ-butyrolactone and ethanolamine, and wherein said reaction productof said γ-butyrolactone and ethanolamine comprisesN-(2-hydroxyethyl)pyrrolidone. .Iadd.
 45. The addition polymerizablecompound of claim 6 or 7 wherein said compound containing one or twoamino nitrogens is an aminoalcohol selected from the group consisting ofethanolamine, diethanolamine, N-methylethanolamine and aminobenzylalcohol. .Iaddend..Iadd.
 46. The method of claim 34 or 35 wherein saidcompound containing one or two amino nitrogens is an aminoalcoholselected from the group consisting of ethanolamine, diethanolamine,N-methylethanolamine and aminobenzyl alcohol. .Iaddend.